Experimental fingerprints of vibrational wave-packet motion during ultrafast heterogeneous electron transfer

被引:157
作者
Zimmermann, C
Willig, F
Ramakrishna, S
Burfeindt, B
Pettinger, B
Eichberger, R
Storck, W
机构
[1] Hahn Meitner Inst Berlin GmbH, D-14109 Berlin, Germany
[2] MPG, Fritz Haber Inst, D-14195 Berlin, Germany
关键词
D O I
10.1021/jp011106z
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
By application of 20 fs laser pulses, vibrational wave packets of low-energy modes (mainly 357 and 421 cm(-1)) were generated in the perylene chromophore that gave rise to periodic beats that lasted longer than I ps in transient absorption signals. Electron transfer from the excited singlet state of the perylene chromophore, attached as molecule DTB-Pe via the -CH2-phosphonic acid group to anatase TiO2, was measured in ultrahigh vacuum with a time constant of 75 fs. The vibrational wave packet that was generated in the donor state continued its motion for several hundred femtoseconds in the product state of the reaction, i.e., in the ionized chromophore. This is direct proof for electron transfer occurring from a nonrelaxed vibrational population that was created by the short laser pulse in the donor molecule. The rise of the product state showed a staircase-like time dependence. The steps are attributed to electron transfer that occurs preferentially each time the vibrational wave packet (frequency 480 cm(-1)) reaches a crossing point for the potential curves of reactant and product state. Such wave-packet modulation of heterogeneous electron transfer can arise if the density of electronic acceptor states in the electrode is changing strongly over an energy range on the order of the reorganization energy below the excited molecular donor orbital.
引用
收藏
页码:9245 / 9253
页数:9
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